JP3400872B2 - Display device - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device in which a first substrate and a second substrate each having an electrode are opposed to each other at regular intervals with a spacer interposed therebetween.

[0002]

2. Description of the Related Art As a display device having such a structure, there are display devices such as liquid crystal (LC), electrochromic (EC), electroluminescence (EL), and plasma, all of which are shown in FIG. The structure shown in the partially enlarged vertical sectional view is adopted. In FIG. 2, 1 is a first substrate (front panel) made of a transparent material such as glass, 2 is a second substrate (back panel) made of a material not necessarily transparent such as glass or ceramics, and 3 is a constant between both substrates. Spacers 4 for holding the intervals of 4 are a plurality of electrodes provided on the first substrate 1, and 5 are counter electrodes provided on the second substrate 2. Reference numeral 6 is a sealing material made of resin or low melting glass. In such a display device, when electricity is applied between the selected electrode 4 and the counter electrode 5, light emission or coloring is caused at a predetermined position by the substrate gap substance 7 such as liquid crystal or plasma held in the substrate gap. It occurs so that a display can be obtained.

Conventionally, as a method of forming spacers for making the intervals between the panels constant, spherical or rod-shaped glass fiber, silica or plastic spacers are dispersed in the substrate gaps, and spacers are formed by printing. The method and the method of mixing alumina powder into the sealing material have been used. However, it is difficult to evenly disperse the spacers by the method of sprinkling spheres or rods made of glass fiber, silica or plastic.
The distance (cell gap) between the two substrates cannot be controlled precisely and uniformly. Further, in this method, the spacers are not necessarily formed at predetermined positions, and the spacers may be scattered on the effective display portion of the substrate, for example, and the area of the effective display portion at that position may be reduced. In a liquid crystal display device, in a light-shielded state, light leakage may occur through a spacer made of transparent glass, silica, plastic, or the like, or by the spacer disturbing the liquid crystal alignment around the spacer. Therefore, it is difficult to realize a high-quality image with high contrast by the method of spraying the spacers. In the case of printing, the spacer has a width of 200 μm and a thickness of 30 μm.
And it was difficult to make the spacer finer and thinner. Further, it is difficult to form a spacer having a uniform thickness by the printing method.

Therefore, as a method for solving the above problems, Japanese Patent Publication No. 02-31368 and Japanese Patent Laid-Open No. 62-91.
No. 9, JP 01-94320, and JP 02
-66519, JP-A-03-288828, JP-A-04-264524, JP-A-04-3
No. 61233, Japanese Patent Laid-Open No. 05-273541,
Japanese Patent Laid-Open No. 05-142550 proposes a method of forming spacers by electrodeposition coating.
Since the spacer of the electrodeposition coating film is formed at a predetermined position on the substrate by the electrodeposition coating method, the above problems can be solved. However, in the methods proposed in these publications, in order to electrodeposit a resin serving as a spacer at a predetermined position, wiring (bus, bus,
An insulating film or a resist is applied on the (bar electrode, source electrode, gate electrode) or on the thin film transistor to perform patterning, and resin is electrodeposited on the patterned exposed portion. In addition, electrodes are patterned in advance, and a resin to be a spacer is electrodeposited on the electrodes exposed by the patterning. These are often electrodes provided in areas other than the area corresponding to the effective display portion. Therefore, the methods proposed in these publications are expected to increase the manufacturing cost of the display device, as compared with the method of forming the spacers by spraying the spacers having a spherical or rod fiber shape.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and a photosensitive resin as a spacer is electrodeposited on at least one substrate,
After that, patterning is performed by photolithography and further heat treatment is performed, whereby a spacer having a uniform film thickness within the substrate surface can be formed at a predetermined position of the substrate at low cost. The display device thus obtained can provide good image quality because the spacers can be formed with a precise and uniform thickness at predetermined positions in the substrate.

[0006]

Means for Solving the Problems In a display device in which a first substrate and a second substrate each having an electrode are opposed to each other with a spacer interposed therebetween at a constant interval, the present inventors have used a spacer made of a photosensitive resin composition. The present invention has been completed by finding that a display device having high image quality can be obtained at low cost by using the display device. That is, the first aspect of the present invention is a display device in which a first substrate and a second substrate each having an electrode are opposed to each other at a constant interval via a spacer, and the spacer is applied on at least one substrate, Patterned into a predetermined pattern by photolithography
(A) Number average molecular weight of 500 to 5,000 and vinyl group
Conjugated diene polymer or copolymer having a content of 50 mol% or more
On the body, its softening point (ring and ball formula of JIS K2531-60
(Softening point method) is higher than 70 ° C.
Addition of a saturated dicarboxylic acid anhydride to a specific
Α, β-non-containing alcoholic hydroxyl group represented by the general formula
Obtained by reacting a saturated monocarboxylic acid derivative
Modified resin 100 parts by weight, and (b) photopolymerization initiator
The present invention relates to a display device comprising a negative photosensitive resin composition of 0.01 to 20 parts by weight . A second aspect of the present invention relates to the first display device of the present invention, wherein the photosensitive resin composition is applied by electrodeposition coating. A third aspect of the present invention is characterized in that the photosensitive resin composition is a thermosetting resin composition, which is patterned by photolithography and then further thermoset. The present invention relates to a second display device. Starting
The fourth item of the present invention relates to any one of the first to third display devices of the present invention, wherein the photosensitive resin composition contains a coloring pigment or a dye. A fifth aspect of the present invention is characterized in that the photosensitive resin composition is patterned in a portion other than an area corresponding to an effective display portion.
It relates to any one of the fourth display devices. The sixth aspect of the present invention is
The present invention is characterized in that a portion other than the area corresponding to the effective display portion is a black matrix portion for shielding light, a thin film transistor portion and / or a wiring portion including a bus bar electrode, a source electrode or a gate electrode. Of the fifth display device.

The present invention will be described in more detail below. The display device of the present invention includes a first substrate and a second substrate each having an electrode.
A substrate is provided, and a gap between the two substrates is filled with a display substance, for example, a substrate gap substance such as liquid crystal or plasma. Specifically, there are display devices using liquid crystal (LC), electrochromic (EC), electroluminescence (EL), plasma, etc., and all of these basically have the structure shown in FIG. have. First, in a display device including a first substrate and a second substrate each having an electrode, at least one of the substrates is subjected to an electrodeposition coating method, a die coating method, a spin coating method,
The photosensitive resin composition is applied by any known application method such as a roll coating method, a dip coating method, and a spray method.
If necessary, both substrates can be coated. When electrodeposition coating is used as the application method, the resin is selectively applied to the conductive part of the substrate, so the amount of photosensitive resin composition used and the amount used in vain are small, saving the photosensitive resin composition. It is preferable for the purpose. Also, electrodeposition coating is more desirable than other coating methods because the coating film thickness is more uniform than other coating methods. Further, in electrodeposition coating, the range in which the film thickness can be accurately controlled is 0.6 to 50 μm, which is wider than other coating methods, and the ferroelectric liquid crystal display device and high-speed STN that require precise control of a narrow gap are required. This is very advantageous when forming a spacer for a display device or the like, or a display device that requires a wider gap than usual.

For electrodeposition coating, the photosensitive resin composition may be a cation type or anion type resin composition, and in the cation type, a composition having a hydrophilic group such as an acid group such as a carboxyl group. When the carboxyl group is neutralized with an inorganic alkali, an organic amine, etc., the above composition becomes water-soluble and electrodeposition coating becomes possible. In the case of the cation type, the photosensitive resin composition is deposited on the anode by electrodeposition. In the anionic type, a basic group such as polyamine is used as the hydrophilic group, and it can be electrodeposited by neutralizing with an acid and solubilizing it in water. In this case, the photosensitive resin composition is deposited on the cathode by electrodeposition. To do. The electrodeposition with the cation-type or anion-type electrodeposition resin composition can be performed by a conventionally known method.

The photosensitive resin composition of the present invention is an etching resistant coating material having a property that its solubility in a solvent is changed by irradiation with light or an electron beam. Any positive-type photosensitive resin which is easily dissolved in the solvent can be used. In particular, a material that is insoluble in liquid crystal after being patterned by photolithography and then cured by heat treatment is preferable. Preferably, the photosensitive resin composition applied by the electrodeposition method is patterned by a photolithography method using exposure and development using an appropriate photomask. That is, patterning is performed by the photolithography method so that the coating film of the photosensitive resin composition covers the area other than the area corresponding to the effective display portion of the substrate. By using this method, a pattern having a desired shape is formed as a spacer, and there is no problem that the spacer interferes with the effective display portion of the substrate. Further, for example, a liquid crystal display device in which a liquid crystal is filled in a gap between two substrates is manufactured by a method of injecting the liquid crystal into the gap after completing the device by combining the two substrates. At this time, according to the present invention, it is possible to perform patterning in consideration of the arrangement and shape of the spacers so that the injected liquid crystal is sufficiently spread over the entire surface of the substrate. For example, in a substrate with electrodes already formed,
When the electrodeposition composition is formed on the electrode by simply energizing the electrode, there is a concern that the injection of the above-mentioned liquid crystal is not always sufficient because the entire electrode portion serves as a spacer. However, according to the method of patterning as in the present invention, the above-mentioned concern is eliminated by taking into consideration the filling condition of the injected liquid crystal, for example, by performing patterning so that the liquid crystal channel is appropriately formed. It

Preferred as the positive type photosensitive resin composition is a photosensitive resin composition comprising quinonediazide, a resin having a hydroxyl group and melamine. Stabilizers, colorants, flame retardants, other additives and the like can be added to the above composition. The colorant is used for preventing light leakage and improving image quality, and a black pigment,
Examples include red pigments, green pigments, blue pigments and the like. The colorant is 0.01 per 100 parts by weight of quinonediazide.
Add ~ 20 parts by weight. Particularly preferable positive-type photosensitive resin compositions include naphthoquinonediazides (naphthoquinonediazide derivatives) as quinonediazides, phenolic resins as hydroxyl group-containing resins, and photosensitive resin compositions containing melamine. When a positive photosensitive resin composition is used in the present invention, the photosensitive resin composition is applied onto a substrate by an appropriate coating method, and then a portion not serving as a spacer is exposed through a photomask and then developed and exposed. Remove the part. By this method, the spacer made of the photosensitive resin composition is formed on the substrate. After that, preferably, the portion to be the spacer is further exposed,
Immediately, it is heated at 70 ° C. to 320 ° C. for 30 minutes to 3 hours to heat-cur the photosensitive composition. When using a photosensitive resin composition consisting of the quinonediazide, a resin having a hydroxyl group and melamine, the acid generated by light irradiation of quinonediazide serves as a catalyst, and the resin having a hydroxyl group and melamine are heat-cured, A spacer having high compressive strength and not dissolving in liquid crystal can be obtained.

The negative photosensitive resin composition used in the present invention is preferably a photosensitive resin composition comprising a resin containing a photopolymerizable functional group such as an acryloyl group or a methacryloyl group and a photopolymerization initiator. Stabilizers, colorants, flame retardants, other additives and the like can be added to the above composition. Examples of colorants include black pigments, red pigments, green pigments, and blue pigments. The colorant is added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the resin containing a photopolymerizable functional group. As the photopolymerization initiator, conventionally known ordinary ones are used, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzyl and Michler's ketone. The photopolymerization initiator is added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the resin. In particular, a photosensitive resin composition comprising (a) a binder polymer containing a photopolymerizable functional group, (b) a photopolymerizable monomer and / or prepolymer (crosslinking agent) and (c) a photopolymerization initiator is preferable. The resin containing a photopolymerizable functional group preferably has thermosetting properties. Examples of the photopolymerizable monomers and prepolymers include polyfunctional acrylates or methacrylates such as trimethylolpropane triacrylate and pentaerythritol tetraacrylate, and prepolymers thereof. These are (a) a binder polymer 1 containing a photopolymerizable functional group.
0.01 to 50 parts by weight is added to 00 parts by weight.

The following are more specific examples of the negative photosensitive resin composition. That is, (a) an adduct obtained by adding an α, β-unsaturated dicarboxylic acid anhydride to a conjugated diene polymer or copolymer having a number average molecular weight of 500 to 5,000 and a vinyl group content of 50 mol% or more, 100 parts by weight of a modified resin obtained by reacting an α, β-unsaturated monocarboxylic acid derivative having an alcoholic hydroxyl group represented by the general formula 2 , and (b) 0.01 to 20 parts by weight of a photopolymerization initiator Is a photosensitive resin composition consisting of parts.

[0013]

[Chemical 2]

The term "conjugated diene polymer or copolymer" as used herein means butadiene and isoprene having 4 or 5 carbon atoms.
Low polymers of conjugated diolefins, or monomers having these conjugated diolefins and other ethylenically unsaturated double bonds, especially isobutylene, diisobutylene, styrene, α-methylstyrene, vinyltoluene, divinyltoluene such as It is a low degree of polymerization copolymer with an aliphatic or aromatic monomer. Also, a mixture of two or more of these can be used. Examples of the α, β-unsaturated dicarboxylic acid anhydride to be added to the conjugated diene polymer or copolymer include acid anhydrides such as maleic anhydride and citraconic acid anhydride. In order to reduce the tackiness of the photosensitive resin coating film before photocuring, the softening point (J
According to the ring and ball softening point measurement method of IS K2531-60)
The acid anhydride is preferably added so that the temperature becomes 70 ° C. or higher.

The α, β-unsaturated monocarboxylic acid derivative having an alcoholic hydroxyl group represented by the general formula 2 is an ester or acid amide of acrylic acid or methacrylic acid. That is, it is an ester with a diol such as ethylene glycol or propylene glycol, or an amide with a hydroxy group-containing primary amine such as methylolamine. Specifically, there are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide and the like, and these can be used alone or in combination.

Α, β-having the above alcoholic hydroxyl group
A modified resin is obtained by reacting an unsaturated monocarboxylic acid derivative with the adduct of the α, β-unsaturated dicarboxylic acid anhydride. In this reaction, the alcoholic hydroxyl group of the α, β-unsaturated monocarboxylic acid derivative having an alcoholic hydroxyl group reacts with the α, β-unsaturated dicarboxylic acid anhydride,
This is opened. This ring-opening produces a carboxyl group, which is used to neutralize the resin with a base such as trimethylamine to make the resin hydrophilic. Therefore, this resin can be subjected to anionic electrodeposition coating. In order to enable electrodeposition, at least 10 mol% of the acid anhydride groups of the above-mentioned adduct are ring-opened.

Further, as the photopolymerization initiator (b), a conventionally known ordinary photopolymerization initiator is used, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzyl and Michler's ketone. The photopolymerization initiator is the above-mentioned modified resin 100.
Add 0.01 to 20 parts by weight to parts by weight. Preferably, a photopolymerizable monomer and / or a prepolymer (crosslinking agent) is further added. Examples of such monomers and prepolymers include polyfunctional acrylates or methacrylates such as trimethylolpropane triacrylate and pentaerythritol tetraacrylate, and prepolymers thereof as described above.

When a negative photosensitive resin composition is used, the photosensitive resin composition is applied onto a substrate by an appropriate coating means, preferably an electrodeposition method, and then a portion to be a spacer, that is, an effective display device. After applying to a portion other than the area corresponding to the display portion, for example, a black matrix portion for the purpose of light shielding, a thin film transistor portion, a wiring portion (bus / bar electrode, source electrode, gate electrode, etc.) or a part thereof, a photomask is applied. And selectively expose it. Next, the unexposed portion is removed by development. In this way, the spacer made of the patterned resin composition is formed. Preferably, further after that 140-
By heating at 280 ° C. for 30 minutes to 3 hours, the vinyl group in the conjugated diene polymer or copolymer is heat-cured,
A spacer having high compressive strength and not dissolving in liquid crystal can be obtained.

The above-mentioned exposure can usually be performed by using an apparatus capable of generating a large amount of ultraviolet rays. For example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metahalide lamp or the like can be used as the light source, but other radiation may be used if necessary. The exposure conditions can be appropriately selected depending on the photosensitive resin composition used, the exposure device, the photomask, and the like.

The conditions for developing the coating film of the photosensitive resin composition are as follows: the amount of exposure of the portion to be selectively removed or the remaining portion, the solubility of the photosensitive resin composition used in the developing solution, and the developing solution. It varies depending on the type and density, the developing time, the developing temperature, etc., and may be selected appropriately. As the developer for the photosensitive resin composition coating film, an aqueous solution in which a basic substance is dissolved can be used, and examples of the basic substance include tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate. , Sodium hydrogen carbonate, sodium metasilicate and the like.

As described above, by using the substrate in which the spacer is provided in the portion other than the area corresponding to the effective display portion of the substrate, the first substrate and the second substrate each having an electrode are provided.
A display device in which the substrate and the substrate are opposed to each other with a spacer interposed therebetween can be assembled by a known method. According to this method, a display device having less variation in cell gap and free from display unevenness, color unevenness, interference fringes, etc. can be obtained. Further, since such a display device does not have a spacer in an effective display portion, it is possible to display a high quality image without deterioration of contrast and light leakage.

[0022]

[Examples] The present invention is described below in a synthesis example (photosensitive resin composition).
(Preparation example of (paint)) and examples will be specifically described. <Synthesis example 1> (Synthesis of photosensitive resin) Using benzyl sodium as a catalyst,
A liquid butadiene polymer having a number average molecular weight of 1,000, a viscosity of 14 poise at 25 ° C. and a 1,2-bond 65% was obtained by polymerizing butadiene at 30 ° C. in the presence of the chain transfer agent toluene. Obtained liquid butadiene polymer 2
86 g, maleic anhydride 214 g, xylene 10 g and antigen 6C (polymerization inhibitor; trade name, Sumitomo Chemical Co., Ltd.)
1.1 g) was placed in a 1-liter separable flask having a reflux condenser and a nitrogen blowing tube, and reacted under a nitrogen stream at 190 ° C. for 4.5 hours. Then, unreacted maleic anhydride and xylene were distilled off to obtain a total acid value of 48
0 mg-KOH / g maleated butadiene polymer was obtained. Softening point of maleated butadiene polymer (ring and ball softening point JI
SK2531-60) was 128 ° C. 200 g of the obtained maleated butadiene polymer, 200 g of diacetone alcohol and 0.2 g of hydroquinone were placed in a 1 liter separable flask having a reflux condenser.
It was immersed in an oil bath at 80 ° C., and the inside of the flask was lightly stirred to completely dissolve the maleated butadiene polymer. Next, 99.3 g of 2-hydroxyethyl acrylate and 12 g of triethylamine were added, and the inside of the flask was vigorously stirred for 20 minutes. As described above, a 2-hydroxyethyl acrylate adduct of a maleated butadiene polymer which is a photosensitive resin was obtained.

(Preparation of Photosensitive Resin Composition (Water Dispersion Paint))
Next, adjust the temperature of the oil bath to adjust the temperature in the flask to 4
The temperature was lowered to 0 ° C., 6 g of benzoin isobutyl ether, 20 g of trimethylolpropane triacrylate and 14 g of trimethylamine were added, and the mixture was stirred for 20 minutes. Then take it out of the oil bath and stir vigorously with pure water 1,46
6 g was gradually added dropwise to prepare a white aqueous dispersion. The aqueous dispersion had a pH of 5.3, an electric conductivity of 1.53 mS, and a nonvolatile content of 16%. The photosensitive resin composition was prepared as described above.

<Synthesis Example 2> (Synthesis of Photosensitive Resin) In the same manner as in Synthesis Example 1, a 2-hydroxyethyl acrylate adduct of a maleated butadiene polymer as a photosensitive resin was obtained. (Preparation of Photosensitive Resin Composition (Paint)) Next, the temperature of the oil bath was adjusted, the temperature inside the flask was lowered to 40 ° C., 6 g of benzoin isobutyl ether was added, and the mixture was stirred for 20 minutes. The non-volatile content of the coating material thus prepared was 45%.

<Synthesis Example 3> (Synthesis of Photosensitive Resin) In the same manner as in Synthesis Example 1, a 2-hydroxyethyl acrylate adduct of a maleated butadiene polymer as a photosensitive resin was obtained. (Preparation of Photosensitive Resin Composition (Water Dispersion Paint)) Next, the temperature of the oil bath was adjusted to lower the temperature inside the flask to 40 ° C.,
6 g of benzoin isobutyl ether, 20 g of trimethylolpropane triacrylate and 14 g of trimethylamine were added and stirred for 20 minutes. Then, the mixture was taken out from the oil bath, and 1,466 g of pure water was gradually added dropwise with vigorous stirring to prepare a white aqueous dispersion. Further, this photosensitive resin composition (aqueous dispersion) was transferred to a sand mill, and 60 g of Daipyroxide Side Black (trade name, manufactured by Dainichiseika Kogyo Co., Ltd.)
Was added under stirring and dispersed while cooling for 5 hours. Next, pure water and triethylamine were added to obtain a black photosensitive resin composition having a pH of 8.0, an electric conductivity of 1.50 mS and a non-volatile content of 12%.

<Synthesis Example 4> Melamine (trade name: MX-45, manufactured by Sanwa Chemical Co., Ltd.) was added to positive photoresist (trade name: OFPR-800, manufactured by Tokyo Ohka Co., Ltd.) to obtain a solid content of the positive photoresist. A positive photosensitive resin composition (paint) was prepared by adding 10% by weight to the above.

Example 1 FIG. 3 is a partially enlarged vertical sectional view of a color filter substrate used in a color thin film transistor (TFT) liquid crystal display device, which is manufactured by an electrodeposition method. In FIG. 3, a black matrix layer (BM) 9, which is a light-shielding portion, and colored layers 10R, 10G, and 10B are formed on a glass substrate 8.
Furthermore, a protective film (overcoat layer) 11 and a transparent conductive film 12 are formed thereon. Using the photosensitive resin composition (water-dispersed paint) prepared in Synthesis Example 1, the transparent conductive film 12 on the color filter substrate was used as an anode, the reticulated stainless steel electrode was used as a counter electrode, and a constant voltage of 20 V was applied on the transparent conductive film 12. For 40 seconds (pressurization time 10 seconds) to form a photosensitive resin composition film having a uniform film thickness. The color filter substrate was washed with pure water and then dried at 80 ° C. for 5 minutes to obtain a photosensitive resin composition film having a uniform film thickness of 5.5 μm and no tack at room temperature.

Then, using a UV exposure machine, a 365 nm ultraviolet ray is applied to the above-mentioned photosensitive resin composition film through a photomask having a light-transmitting pattern of 20 μm diameter for exposing only a part of the black matrix layer 9 of the color filter substrate. Irradiation was performed at an intensity of 150 mJ / cm ² . When the photosensitive resin composition film was developed with a 1% KOH aqueous solution, the transparent conductive film 12
A spacer of the photosensitive resin composition was patterned on a part of the portion above and below which the black matrix layer 9 was present. After the color filter substrate having the spacers patterned was washed with pure water, the spacers made of the photosensitive resin composition were further heat-cured at 180 ° C. for 2 hours. As a result, the compressive strength is high and the elastic height is 5μ.
m resin spacers were obtained. FIG. 1 is a partially enlarged cross-sectional view of a color filter substrate provided with a resin spacer. A resin spacer 13 is formed on a portion of the color filter substrate corresponding to the black matrix layer 9 on the transparent conductive film 12. The spacer of the photosensitive resin composition was not dissolved in the liquid crystal, and it was not observed that the ionic impurities affecting the display performance were dissolved in the liquid crystal from the spacer. When a TFT liquid crystal display device was assembled using the color filter substrate having the resin spacer obtained as described above, there was little variation in cell gap, and as a result, a display device without display unevenness, color unevenness, interference fringes, etc. was gotten. Further, since this TFT liquid crystal display device does not have a spacer in the effective display portion, a high quality image is displayed without deterioration in contrast, light leakage, and deterioration in image quality due to alignment defects at the spacer interface.

Example 2 On the transparent conductive film of the color filter substrate prepared by the pigment dispersion method, the black matrix layer as the light shielding layer, the coloring layer, the protective film and the transparent conductive film were formed, and the synthesis example 2 was obtained. The photosensitive resin composition (coating material) prepared in (3) was applied with a spin coater to a film thickness of 5.5 μm. Next, using a UV exposure device, through a photomask having a light transmission pattern of 5.0 μm in diameter, which exposes only a part of the black matrix layer of the color filter, the photosensitive resin composition film is exposed to ultraviolet rays of 365 nm at 500 mJ / cm 2. Irradiation with an intensity of ² . When the photosensitive resin composition film was developed with a 2.48% tetramethylammonium hydroxide aqueous solution, a spacer of the photosensitive resin composition was formed on a part of the transparent conductive film and under the black matrix. Patterned. After the color filter substrate having the spacers patterned was washed with pure water, the spacers made of the photosensitive resin composition were further heated and cured at 220 ° C. for 2 hours. As a result, a resin spacer having a high compressive strength and elasticity and a height of 5 μm was obtained. Further, the spacer of the photosensitive resin composition was not dissolved in the liquid crystal, and it was not observed that ionic impurities affecting display performance were dissolved out of the spacer in the liquid crystal. When a TFT liquid crystal display device was assembled using the color filter substrate having the photosensitive resin composition spacer obtained as described above, there were few variations in cell gap, and as a result, display unevenness, color unevenness, interference fringes, etc. No display was obtained. Further, since this TFT liquid crystal display device does not have a spacer in the effective display portion, a high quality image is displayed without deterioration in contrast, light leakage, and deterioration in image quality due to alignment defects at the spacer interface.

<Third Embodiment> FIG. 4 is a partially enlarged perspective view of an array substrate of a TFT liquid crystal display device. In FIG.
The TFT 14, the pixel electrode 15, the gate bus wiring 16, and the source bus wiring 17 are formed on the glass substrate. The photosensitive resin composition (water-dispersed paint) prepared in Synthesis Example 3 was used, and the gate bus wiring 16 and the source bus wiring 17 of this array substrate were used as anodes, and the reticulated stainless steel electrodes were used as counter electrodes, and the gate bus wiring and source bus were used. 20 on the wiring
Electrodeposition was performed at a constant voltage of V for 20 seconds (pressurization time was 10 seconds) to form a photosensitive resin composition film having a uniform film thickness. After the array substrate was washed with pure water and dried at 80 ° C for 5 minutes,
A photosensitive resin composition film having a uniform film thickness of 6.0 μm without tack at room temperature was obtained.

Then, using a UV exposure machine, through the photomask having a pattern for exposing only a part of the gate bus wiring and the source bus wiring, the above-mentioned photosensitive resin composition film is irradiated with an ultraviolet ray of 365 nm at an intensity of 360 mJ / cm ² . Illuminated. When the photosensitive resin composition film was developed with a 2.48% tetramethylammonium hydroxide aqueous solution, spacers of the photosensitive resin composition were patterned on a part of the gate bus wiring and the source bus wiring. After washing the array substrate with the patterned spacers with pure water,
Further, the spacer made of the photosensitive resin composition was heated and cured at 250 ° C. for 2 hours. As a result, a resin spacer having a high compressive strength and elasticity and a height of 5.5 μm was obtained. FIG. 5 is a partially enlarged perspective view of an array substrate provided with a resin spacer. Array board gate bus wiring 16
The resin spacer 13 is formed on a part of the source bus line 17. In addition, the above-mentioned spacer is Daipyroxide side black (trade name, Dainichi Seika Kogyo Co., Ltd.
(Manufactured by Co., Ltd.). When its conductivity was measured, it was an insulator. Further, the spacer of the photosensitive resin composition was not dissolved in the liquid crystal, and it was not observed that ionic impurities affecting display performance were dissolved out of the spacer in the liquid crystal. When the TFT liquid crystal display device was assembled using the array substrate having the resin spacers obtained as described above, there was little variation in the cell gap, and as a result, a display device without display unevenness, color unevenness, interference fringes, etc. was obtained. Was obtained. Also this T
Since the FT liquid crystal display device does not have a spacer in the effective display portion, a high quality image is displayed without deterioration in contrast, light leakage, and deterioration in image quality due to alignment defects at the spacer interface.

<Embodiment 4> FIG. 6 is a partial perspective view of a simple matrix liquid crystal display device. In FIG. 6, the liquid crystal display device is formed of two glass substrates 8 on which scan electrodes 18 and data electrodes 19 are patterned. Using the photosensitive resin composition (water-dispersed paint) prepared in Synthesis Example 1, one of two glass electrodes, in this example, the transparent conductive film as the data electrode 19 was used as the anode, and the reticulated stainless steel electrode was used as the counter electrode. As 2 on the transparent conductive film of the data electrode
Electrodeposited at a constant voltage of 0V for 40 seconds (boosting time 10 seconds),
A photosensitive resin composition having a uniform film thickness was formed into a film. The substrate on the data electrode side was washed with pure water and then dried at 80 ° C. for 5 minutes to obtain a photosensitive resin composition film having a uniform film thickness of 5.5 μm and no tack at room temperature.

Next, using a UV exposure device, a part of the data electrode (a part which is not an effective display part, that is, a part which faces a part which is not a scanning electrode when the liquid crystal cell is assembled).
Through the photomask having a pattern that exposes only the above, the photosensitive resin composition film is exposed to ultraviolet light of 365 nm at 300 nm.
Irradiation was performed at an intensity of mJ / cm ² . When the photosensitive thermosetting resin film was developed with a 1% sodium carbonate aqueous solution, it was exposed to a portion of the data electrode that was not an effective display portion on the transparent conductive film, that is, a portion facing a portion that was not the scanning electrode when the liquid crystal cell was assembled. The spacer of the resin composition was patterned. After washing the data electrode side substrate having the spacers patterned with pure water, the spacers made of the photosensitive resin composition were further heat-cured at 200 ° C. for 2 hours. As a result, a resin spacer having a high compressive strength and elasticity and a height of 5 μm was obtained. FIG. 7 is a partially enlarged perspective view of a data electrode of a simple matrix liquid crystal display device provided with a resin spacer. In FIG. 7, a resin spacer 13 is provided on the data electrode 19 on the glass substrate 8. Further, the spacer of the photosensitive resin composition was not dissolved in the liquid crystal, and it was not observed that ionic impurities affecting display performance were dissolved out of the spacer in the liquid crystal. When a simple matrix liquid crystal display device was assembled using the substrate on the data electrode line electrode side having the resin spacer obtained as described above, the cell gap variation was small, and as a result, display unevenness, color unevenness, and interference fringes were observed. A display device without Further, since this simple matrix liquid crystal display device does not have a spacer in the effective display portion, a high quality image is displayed without deterioration in contrast, light leakage, and deterioration in image quality due to alignment defects at the spacer interface.

<Embodiment 5> A portion of a scanning line electrode used in a simple matrix liquid crystal display device similar to that in Embodiment 4 (a portion which is not an effective display portion, that is, a portion which faces a portion which is not a data line electrode when a liquid crystal cell is assembled). ), A resin spacer was prepared in the same manner as in Example 4, and a simple matrix liquid crystal display device was assembled. This simple matrix display device has less variation in cell gap,
As a result, the display device was free from display unevenness, color unevenness, and interference fringes. In addition, this simple matrix liquid crystal display device,
Since there is no spacer in the effective display area, good image quality is displayed without deterioration of contrast, light leakage, and deterioration of image quality due to alignment defects at the spacer interface.

<Embodiment 6> A portion of a data line electrode used in a simple matrix liquid crystal display device similar to that in Embodiment 4 (a portion which is not an effective display portion, that is, a portion which faces a portion which is not a scanning line electrode when a liquid crystal cell is assembled). ) And a part of the scanning line electrode (a part which is not an effective display part, that is, a part which faces a part which is not a data line electrode when the liquid crystal cell is assembled), a resin spacer is formed by the same method as in Example 4, A simple matrix liquid crystal display device was assembled. This simple matrix display device has less variation in cell gap, resulting in display unevenness, color unevenness,
It was a display device without interference fringes. Further, since this simple matrix liquid crystal display device does not have a spacer in the effective display portion, a high quality image is displayed without deterioration in contrast, light leakage, and deterioration in image quality due to alignment defects at the spacer interface.

<Example 7> The same color filter substrate as that used in Example 1 was used, and the transparent conductive film on the color filter substrate was used as the anode and the mesh stainless steel electrode was used as the counter electrode. The photosensitive resin composition (water-dispersed coating material) prepared in Synthesis Example 1 was electrodeposited at a constant voltage of 30 V for 200 seconds (pressurization time 10 seconds). After the color filter substrate was washed with pure water and dried at 80 ° C for 10 minutes, it had a uniform film thickness of 21μ without tack at room temperature.
A photosensitive resin composition film having m was obtained.

Next, using a UV exposure device, only a part of the black matrix layer of the color filter is exposed 3
Through a photomask with a light transmission pattern of 5 μm diameter,
The above-mentioned photosensitive resin composition film was exposed to ultraviolet rays of 365 nm at 45 nm.
Irradiation was performed at an intensity of 0 mJ / cm ² . 1% of photosensitive resin composition film
When developed with an aqueous solution of sodium carbonate, a spacer of the photosensitive resin composition was patterned on a part of the portion on the transparent conductive film where the black matrix layer was present. After the color filter substrate having the spacers patterned was washed with pure water, the spacers made of the photosensitive resin composition were further heat-cured at 200 ° C. for 3 hours. As a result, the compressive strength is high and the elastic height 20
A resin spacer of μm was obtained. Further, the spacer of the photosensitive resin composition was not dissolved in the liquid crystal, and it was not observed that ionic impurities affecting display performance were dissolved out of the spacer in the liquid crystal. When a polymer dispersion type TFT liquid crystal display device was assembled using the color filter substrate having the resin spacer obtained as described above, there was little variation in cell gap, and as a result, display unevenness, color unevenness, interference fringes, etc. A display device without the above was obtained.

Example 8 On the transparent conductive film of the color filter substrate prepared by the pigment dispersion method, the black matrix layer which is the light shielding layer, the coloring layer, the protective film and the transparent conductive film are formed, and then, Synthesis Example 4 is prepared. The photosensitive resin composition (coating material) prepared in (3) was applied with a spin coater to a film thickness of 5.5 μm. Then, using a UV exposure machine, through the photomask having a pattern in which a part of the black matrix layer of the color filter is left exposed and the other part is exposed, the photosensitive resin composition film is exposed to 400 mJ / cm ² of ultraviolet light of 365 nm. Irradiation with the intensity of. When the photosensitive resin composition film was developed with a 2.48% aqueous solution of tetramethylammonium hydroxide, the photosensitive resin composition in the exposed area was removed by development, and the unexposed area was formed on and below the transparent conductive film. The photosensitive resin composition remained on a part of the portion where the black matrix layer was present. 400mJ / c on this substrate
The entire surface was exposed by irradiating the ultraviolet ray having an intensity of m ² and immediately after that, the substrate was heated at 250 ° C. for 2 hours. As a result, a resin spacer having a high compressive strength and elasticity and a height of 5 μm was obtained. Further, when the solubility of the spacer of the photosensitive resin composition in the liquid crystal was examined, it was insoluble in the liquid crystal. When a TFT liquid crystal display device was assembled using the color filter substrate having the photosensitive resin composition spacer obtained as described above, there were few variations in cell gap, and as a result, display unevenness, color unevenness, interference fringes, etc. No display was obtained. In addition, since this TFT liquid crystal display device does not have a spacer in the effective display portion, a high quality image is displayed without deterioration of contrast, light leakage, and deterioration of image quality due to alignment defects at the pacer interface.

[0039]

Since the spacer between the electrode substrates is formed by applying the photosensitive resin composition on the substrate and then patterning it by the photolithography method, the display device of the present invention has a cell gap of Little variation,
As a result, it is possible to provide display quality with less display unevenness, color unevenness, interference fringes, and the like. In addition, in this display device, a spacer can be created at a designated place, and since there is no spacer in the effective display portion, there is no decrease in contrast and light leakage. It is possible to display a high quality image without deterioration of the image quality due to the liquid crystal alignment defect. When the electrodeposition technique is used as the coating method of the photosensitive resin composition, the cell gap can be further reduced and the spacer can be formed at low cost.

[Brief description of drawings]

FIG. 1 is a TFT provided with a resin spacer according to the present invention.
FIG. 3 is a partially enlarged vertical sectional view of a color filter substrate of a liquid crystal display device.

FIG. 2 is a partially enlarged vertical sectional view showing the structure of a conventional display device.

FIG. 3 is a partially enlarged vertical sectional view of a color filter substrate of a TFT liquid crystal display device.

FIG. 4 is a partially enlarged perspective view of an array substrate of a TFT liquid crystal display device.

FIG. 5: TFT provided with a resin spacer according to the present invention
FIG. 3 is a partially enlarged perspective view of an array substrate of a liquid crystal display device.

FIG. 6 is a partial perspective view of a simple matrix liquid crystal display device.

FIG. 7 is a partially enlarged perspective view of a data electrode of a simple matrix liquid crystal display device provided with a resin spacer according to the present invention.

[Explanation of symbols]

1st substrate 2 Second substrate 3 spacers 4 electrodes 5 Counter electrode 6 Sealant 7 Substrate interstitial material 8 glass substrates 9 Black Matrix (BM) 10R, 10G, 10B colored layer 11 Protective film 12 Transparent conductive film 13 Spacer of photosensitive resin composition 14 Thin film transistor (TFT) 15 pixel electrodes 16 gate bus wiring 17 Source bus wiring 18 scanning electrodes 19 Data electrode

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Iizuka 4-59 Komukainishimachi, Saiwai-ku, Kawasaki City, Kanagawa Prefecture (56) Reference JP-A-1-134336 (JP, A) JP-A-3-182718 (JP , A) JP 3-2833 (JP, A) JP 4-178628 (JP, A) JP 4-21822 (JP, A) JP 6-67135 (JP, A) JP 5-313124 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G02F 1/1339

Claims (6)

(57) [Claims] 1. A display device in which a first substrate and a second substrate each having an electrode are opposed to each other with a spacer interposed therebetween at a constant interval, the spacer being coated on at least one substrate, and then by photolithography. (A) Number average molecular weight 500 patterned into a predetermined pattern
~ 5,000 and vinyl group content of 50 mol% or more
The diene polymer or copolymer has a softening point (JIS
K2531-60 ring and ball softening point method) is 70 ° C.
As described above, α, β-unsaturated dicarboxylic acid anhydride
Alcohol represented by the following general formula 1 is added to the added product.
Derivatives of α, β-Unsaturated Monocarboxylic Acids Containing Hydrophilic Hydroxyl Group
100 weight of modified resin obtained by reacting the body
Parts and (b) 0.01 to 20 parts by weight of a photopolymerization initiator
A display device comprising a negative photosensitive resin composition comprising [Chemical 1] 2. The display device according to claim 1, wherein the photosensitive resin composition is applied by electrodeposition coating. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a thermosetting resin composition, which is patterned by photolithography and then further thermoset. Display device. 4. A display device according to any one of claims 1-3, wherein the photosensitive resin composition is characterized in that it comprises a colored pigment or dye. Wherein said photosensitive resin composition, a display device according to any one of claims 1 to 4, characterized in that patterned into portions other than the area corresponding to the effective display portion. 6. A portion other than the area corresponding to the effective display portion, a black matrix portion for the purpose of shielding, thin film transistor portion and / or bus bar electrodes, that is a wiring portion including a source electrode or a gate electrode The display device according to claim 5 , wherein the display device is a display device.